CA1101154A

CA1101154A - Disperse azo dyestuffs

Info

Publication number: CA1101154A
Application number: CA302,224A
Authority: CA
Inventors: John H. Moore; Brian R. Fishwick; George A. Bennett; Robert D. Mcclelland
Original assignee: Imperial Chemical Industries Ltd
Current assignee: Syngenta Ltd
Priority date: 1977-04-28
Filing date: 1978-04-28
Publication date: 1981-05-19
Also published as: JPS626592B2; MX148450A; CH633576A5; FR2388861A1; ES469268A1; JPS53137229A; FR2388861B1; HK61981A; BR7802641A; DE2818653A1; PT67962B; NL7804338A; PT67962A; IT7822839A0; IT1094970B; DE2818653C2

Abstract

ABSTRACT OF THE DISCLOSURE

Dyestuff mixtures comprising two or more monoazo disperse dyestuffs of the formula

Description

1~01154 This invention relates to disperse azo dyestuffs and more particularly to mixtures of two or more disperse monoazo dyestuffs of closely related structure, to a process of manufacture of the said mixtures and to the application of the said mixtures to aromatic polyester textile materials and aromatic polyester/cellulose unions According to the present invention there is provided a mixture of two or more monoazo dyestuffs of the formula:

2 ~ ~ \

W ~HCOR
' ' ".
wherein W is a chlorine atom or a bro~ine atom;
X is hydrogen or -OR and R, R , Z and Y are lower alkyl groups;
:: . provided that the mixture contains at least one component in which X = H and another in which X=OR .
Throughout this specification by "lower alkyl group"
we mean an alkyl group containing from 1 to 4 carbon atoms As specific examples of lower alkyl groups represented by R, R , Y and æ there may be mentioned methyl ethyl, ~: 20 n-propyl, isopropyl, n-butyl, sec-butyl and isobutyl groups, b~ ~
' . ' ' ' :

11C~1154 In the case in which the mixture of dyestuffs as deined above comprises two components, then these components may be present in the mixture in amounts from 95:5 to 5:95 parts by weight, preferably from 20:80 to 80:20 parts by weight, When three or more component dyestuffs are present in the mixture, no single dyestuff will comprise less than 5% by weight of the total weight of the mixture.
A preferred mixture of dyestuffs according to the 10 invention is that comprising two dyestuffs having the formula:

2 xl / 2 5 2~ =R ~ ~

`
: ~' , .
: : ~ in which the two dyestuffs have W = Br, X = H and W = Br, X = methoxy respectively, : Another preferred mixture of dyestuffs according ,. :
to the invention is that comprising two dyestuffs of formula (II) in which W~= Br, X = H and W = Br, Xl = ethoxyt respectively, : :Yet another preferred mixture of dye~tuffs according : -~;~ 2~0 to~the~invention:is ;that comprising two dyestuffs of formula (II) in which W:= Cl, X = H and W = Cl, Xl = methoxy, respectively.
, ::: ~ ~: : ' ~ 2-., :
"~L7' ,: ; : ~ .: :
- . . .
,,.
. . - . . , . . ~ - ' . : : - :

llQllS4 Still another preferred mixture of dyestuffs accord-ing to the invention is that comprising two dyestuffs of formula (II) in which W = Cl, Xl = H and W = Cl, Xl = ethoxy, respectively It is further preferred that in each of the above-defined mixtures the dyestuffs of formula (II) in which Xl =
H and the dyestuff of formula (II) in which Xl is either methoxy or ethoxy should be in the proportions between approximately 4:1 and approximately 2:1 by weight, respectively Particularly preferred is a mixture comprising two dyestyfs of formula ~II) in which W = Br, X = H and W =
Br, Xl = methoxy, in the proportions of approximately 3:1 by weight respectively.
According to a further feature of the invention there is provided a process for the manufacture of the ~:~ - mixtures o disperse monoazo dyestuffs of formula (I) which comprises coupling a mixture of at least two coupling .
~components of formula X ' : NHCOR
wherein R, X, Y:and Z have the meanings stated above, with a~t least one diazonium compound obtained by diazotisation of an amine of the formula: ~

., - ~ .
-: . ~: , :
~ 3-.

h .
.

~2 2~ 2 (IV) W

wherein W has the meaning stated above, provided that the mixture of coupliny components contains at least one com-ponent in which X is hydrogen and at least one component in which X is o~ .
In the case in which two diazonium compounds are employed in a process as defined above, these may be used by individually diazotising the amines and adding ~he dia-zonium compounds so obtained simultaneously or consecutively to the mixture of coupling components, or the amines may be diazotised in admixture and the mixed diazonium compounds ' ~ so obtained then added to the mixture of coupling components, or the individually prepared diazonium compounds may be mixed together before addition to the mixture of coupling :`: components, :The amine of formula (IV) may be 2, 4-dinitro-6-chloroaniline or 2,4-dinitro-6-bromoaniline, Examples of coupling components of formula (III) -:
: are 5-acetylamino-2-methoxy-N,N-diethylaniline, N,~-diethyl-m-aminoacetani;lide,~ The diazotisation and coupling may be :~
carried out by methods conventionally used for these reactions. Thus diazotisation of the amine or amines of formula ~IV) may be carried out in nitrosylsulphuric acid in known manner, followed by addition of the resulting solution of the diazo compound to a solution or suspension : : ~ of the coupling components in water or in a mixture of water : ~ ~
.' ~ , ' :
-. . .
.~, . . . .
. .
, . ' . i . . ~: . ' .: : . ~

11(~1154 and a water-miscible organic liquid, if necessary adjusting the pH of the mixture to facilitate the coupling reaction, and finally isolating the resulting dyestuff by conventional methods.
In addition to preparing mixtures of dyestuffs according to the invention from mixed coupling components and a single diazo component or mixture of diazo components as defined above, such mixtures may of course be obtained - by mixing together the individually prepared component dye-stuffs of the mixture, obtained by conventional diazotisation and coupling reactions from an amine of formula (IV) and a coupling component of formula (III) The dyestuffs may be applied to polyester textile materials by aqueous dyeing, padding or printing methods in the form of aqueous dispersions which are prepared by conventional methods, for example, by milling the dyestuffs with water and a suitable dispersing agent such as the :~ sodium salt of a naphthalene-2-sulphonic acid/formaldehyde : condensate, and this colouration process constitutes a ::. 20 further feature of the invention The dyestuff mixtures of the present invention , provide navy shades on aromatic polyester textile materials which have very good build-up properties and high tinctorial ~: ; strength superior to the effect achieved by the application of any single component of the dyestuff mixture on its own.
:. :
According to a yet further feature of the invention there is provided a process.for the colouration of aromatic polyester/cellulose unions which comprises applying to the said unions by an aqueous dyeing, padding or printing 30. : process a:mixture of two or more disperse monoazo dyestuffs ;~ ~ - as hereinbe:fore defined.

~ _5_ .

' ~ ' ' ' ' . - ' ' , It is known that the polyester component of a polyester/cellulosic blend can be dyed with disperse dyes, but these dyes suffer from the disadvantage that, particularly when applied by a padding or printing process, they also adhere to the cellulosic component. Because disperse dye-stuffs have low fastness properties on cellulosic materials, that portion of the applied dyestuffs which has stained the cellulose is easily washed off and fades rapidly on exposure to light. Consequently a polyester/cellulose union coloured in this way has poor fastness properties due to loose dye on - the cellulose, In order that the coloured union has the maximum fastness properties it is essential that any unfixed dyestuf f be removed. This is usually achieved by a "reduction clear" treatment of the coloured union (i,e, a treatment in a warm aqueous alkaline solution of sodium hydrosulphite). However, the disposal of the liquors from ; ~ the "reduction clear" treatment causes ecological problems due to the presence of the reducing agent, Also a reduction clear treatment cannot be used after the cellulose poxtion of the blend has been dyed with a dye which is sensitive to this treatment, Further, in the absence of a "reduction clear"
treatment, any dyestuff which is removed by, for example, an~ordinary washing treatment can give rise, especially in the case of printing, to back staining resulting in the " ~ . ~
staining of other ~areas of the print, or dull tones.
The above described problems are minimised by the use of mixtures o~ disperse monoazo dyestuffs as herein-i: :
before d~fined, which cause a minimum of staining of the ; ~cellulose portion of ths blend, ~ :
~ 6-:: : .
-:, ~ ~ , .

- : . - , .

ll~llS4 The process may be carried out by immersing the polyester/cellulose union in a dyebath comprising an aqueous dispersion of the two or more monoazo dyestuffs as defined above, which dyebath preferably contains a non-ionic, cationic and/or anionic surface-active agent, and thereafter heating the dyebath for a period at a suitable temperature, The dyeing process can either be carried out at a temperature between 95 and 100C, preferably in the presence of a carrier such as diphenyl,o-hydroxydiphenyl, methyl naphthalene, methyl salicylate or trichlorbenzene, or at a temperature from 120C to 140C, under superatmospheric pressure, The process of the invention may also be carried out by padding on to the polyester/cellulose union an aqueous dispersion of two or more disperse monoazo dyestuffs as here-inbefore defined, the dyestuffs then being fixed on the union by steaming it for short periods at a temperature between 100 and 180C or baking it at temperatures between 160 i and 220C, If desired the padding liquor can contain the : conventional additives, for example, dispersing agents, thickeners, migration inhibitors or urea, As a further method of application a thickened : printing paste containing the two or more disperse monoazo dyestuffs~in dispersed form can be applied to the surface of ~ the polyesterjcellulose union by any of the methods ': , conventionally used for applying printing pastes to textile : materials, for example by block, screen or roller printing, The printed textile material~ optionally after being dried, `then steamed for short periods at temperatures between :
.
~ ~ 100 and 180C, or is baked at temperatures between 160C

:~ 30 and 220C.~ Suitable thickening agents which are present in ~: the printi~ng paste include gum tragacanth, gum arabic, alginates, for example, sodium or ammonium alginates, oil-.
: ~ in-water or water-in-oil emulsions, or thickening agents of . ~ -7-, -, " ll(~llS4 synthetic origin based on ethylene/maleic anhydride copolymers or polyacrylic acids The printing pastes can also contain conventional additives such as urea, sodium m-nitrobenzene sulphonate, diimides, acids or alkalis to assist in bringing about fixation of the various dyestuffs.
After the dyeing, padding or printing process has been carried out, the coloured textile material is then rinsed in water.
The aromatic polyester/cellulose unions used in the process of the invention can be any textile materials which are mixtures of aromatic polyester fibres and cellulose fibres. Such unions are usually in the form of knitted, or preferably woven goods. The percentage of aromatic polyester fibres is usually in the range of 20 to 95%, and preferably 30 to 85%, by weight of the weight of the union The aromatic polyester fibres are preferably polyethylene terephthalate fibres and the cellulose fibres '~ are preferably cotton, linen, viscose rayon or polynosic ~ rayon fibres, By the use of mixtures of disperse monoazo dyestuffs as hereinbefore defined in the process of the invention the aromatic polyester part of the polyester/cellulose union is coloured in navy shades with excellent reserve of the cellulose part of the union, i.e. the cellulose remains uncoloured or virtually so Any staining of the cellulose ~which does occur can be removed by a "reduction clear"
treatment which is very much milder than that conventionally ; employed, with a corresponding reduction in the effluent disposal problem The process of the present invention can also be appl1ed to the colouration of unions containing aromatic ~' ' .

, 11~1154 polyester and cellulose whereby the mixture of disperse monoazo dyestuffs as hereinbefore defined is applied in conjunction with one or more suitable colouring matters for the cellulose, and this constitutes a still ~urther feature of the invention.
Suitable colouring matters for the cellulose part of the polyester/cellulose unions are Direct Dyestuffs, Vat Dyestuffs, Sulphur Dyestuffs, Azoic Colouring Matters, or Reactive Dyestuf~s.
The mixture of disperse monoazo dyestuffs for the -~
aromatic polyester part of the union and a colouring matter from one of the above-defined classes for the cellulose part of the union may in general be applied concurrently or consecutively, by the conventional processes.
Though the dyes employed in this invention can be applied to a polyester/cellulosic blend by all conventional processes and together with all classes of dyes for cellulose, ;~ a particular advantage of these dyes is that since they have good cellulose reserve and dyeings of high fastness can be obtained using processes which do not involve a reduction clearing treatment. This permits the use of simple and economical processes, as exemplified below, Thus, the polyester!cellulosic material may be padded with a liquor containing disperse and reactive dyes, dried, baked or steamed at high temperature to fix the disperse dyes on the polyester component, padded in aqueous alkali, :
steamed to fix the reactive dye on the cellulosic component, washed and dried.

Alternatively, the pad liquor can contain alkali, 30 ~ and fixation of the reactive dye be achieved during drying _ g_ .~

llQ1154 prior to baking, thus avoiding the need for an alkali pad-steam treatment, In batchwise processing the polyester component can be dyed in any conventional manner, the dyeing given a mild reduction clearing treatment, or no treatment at all, the cellulosic portion then being dyed by any process, using any class of dye for ~ellulose.
The cellulosic portion can first be dyed with a reactive dye, the material rinsed until neutral, and the polyester component then dyed with the mixture of disperse dyes in a separate dyebath either under pressure or with a carrier, washed and dried. Or the cellulose can be dyed first with a reactive dye, after which the mixture of disperse dyes is added to the exhausted dyebath, the pH
adjusted and any auxiliary products added, and the polyester component dyed either at the boil with a carrier, or under pressure.
The reactive dyestuffs used in the process of the invention can be any water-soluble dyestuffs which contain at least one fibre-reactive group, this being defined as ~ a group whose presence in the dyestuff molecule renders `~ the dyestuff capable of chemically combining with hydroxy groups present in cellulose textile materials so that the dyestuff molecule becomes attached to the cellulose molecule through a covalent chemical bond or bonds. Each fibre-reactive group is attached to a carbon atom pxesent in the dyestuff molecule and preferably to a carbon atom of an aromatic ring, preferably a benzene ring, present in the dyestuff molecule. The said dyestuffs are preferably dye-stuffs of the azo, including monoazo and polyazo and metallised azo dyes, anthraquinone, formazan, triphendioxazine, nitro and phthalocyanine series containing at least one fibre-reactive group, l~Q11~4 As examples of fibre-reactive groups there may be mentioned acylamino radicals derived from olefinically unsaturated aliphatic carboxylic acids such as acryloylamino and crotonylamino, or from halogen-substituted aliphatic carboxylic acids such as ~-chloropropionylamino, ~-bromo-propionylamino, ~ -trichlorocrotonylamino and tetra-fluorocyclobutylacryloylamino Alternatively the fibre-reactive group can be a vinyl sulphone, ~-chloroethyl sul-phone, ~-sulphatoethylsulphonyl, ~-chloroethylsulphonamide or an optionally N-substituted ~-aminoethylsulphonyl group The fibre-reactive group is preferably a heterocyclic radical having two or three nitrogen atoms in the hetero-cyclic ring and at least one labile substituent attached to a carbon atom of the heterocyclic ring As examples of labile substituents there may be mentioned chlorine, bromine, fluorine, quaternary ammonium groups, thiocyano, sulphonic acid, hydrocarbylsulphonyl groups, groups of the formula -SC - N wherein the .~ . S
nitrogen atom carries optionally substituted hydrocarbon ; 20 or heterocyclic radicals, and groups of the formula:--- S -- C `~

\ S ,_ wherein the dotted line indicates the atoms necessary to form an optionally substituted or fused heterocyclic ring.

, 11~1154 As specific examples of such fibre-reactive heterocyclic radicalst there may be mentioned 3:6-dichloro-pyridaæine-4-carbonylamino, 2:3-dichloroquinoxaline-5- or 6-(sulphonyl or carbonyl)amino, 2:4-dichloroquinazoline-6-or 7-sulphonylamino, 2:4:6-trichloroquinazoline-7- or 8-sulphonylamino, 2:4:7- or 2:4:8-trichloroquinazoline-6-- sulphonylamino, 2:4-dichloroquinazoline-6-carbonylamino, 1:4-dichlorophthalazine-6-carbonylamino, 4:5-dichloro-pyridazon-l-ylamino, 2:4-dichloropyrimid-5-yl-carbonylamino, : . 10 1-(phenyl-4'-carbonylamino)-4:5-dichloxopyridazone, 2:4-and/or 2:6-dichloro- or bromo-pyrid-6-(and/or -4)ylamino, difluorochloro-pyrimidylamino, trichloropyrimidylamino, tribromopyrimidylamino, dichloro-5-(cyano, nitro, methyl or carbomethoxy)pyrimidylamino, 2-methylsulphonyl-6-chloropyrimid-4-ylcarbonylamino and 5-chloro-6-methyl-2-methylsulphonylpyrimid-4-ylamino, and more particularly . 1:3:5-triazin-2-ylamino radicals which contain a fluorine ~.
,~ or a bromine and, above all, a chlorine atom on at least one of the 4- and 6- positions, for example 4:6-dichloro-1:3:5-triazin-2-ylamino When the triazine nucleus contains only a single halogen atom, preferably a chlorine atom, then the third carbon atom of the triazine ring can be : substituted by a hydrocarbon radical, such as methyl or : phenyl, but more particularly by an optionally substituted hydroxy, mercapto or amino group, such as methoxy, phenoxy, ; : a- and ~-naphthoxy, methylmercapto, phenylthio, methylamino, diethylamino, cyclohexylamino and anilino and ~-alkylanilino and substituted derivatives thereo~ such as anisidino, toluidino, carboxylanilino, sulphoanilino, disulphoanilino and sulphonated naphthylamino.

.

.
.. ... .

Thus a preferred class of the reactive dyestuffs comprises those dyestuffs which contain as the fibre~reactive group a group of the formula:

~ `\
Cl - C C - N -N ~ Cr_lH2r_ ~ C/

Q
wherein r is 1 or 2, and Q is a chlorine atom, an optionally substituted amino group or an etherified hydroxyl group.
The optionally substituted amino groups represented by Q are preferably optionally substituted alkylamino, anilino, or ~-alkylanilino groups, e g, methylamino, ethyl-amino, ~-hydroxyethylamino, di(~-hydroxy-ethyl)amino, ~-methoxyethylamino, ~-sulphatoethylamono, o-, m- and ~-sulphoanilino, 4- and 5-sulpho-2-carboxyaniline, 4- and 5-sulpho-2-methoxyanilino, 4- and 5-sulpho-2-methylanilino, 4-and 5-sulpho-2-chloroanilino, 4- and 5-sulpho-2-chloro-anilino, 2,4-, 2,5- and 3,5-disulphoanilino, N-methyl-m-and p-sulphoanilino.
If desired the fibre-reactive group can be of the type:
~H Jl M J2 wherein Jl is a pyrimidine or triazine ring optionally carrying a labile substituent, J is a pyrimidine or tria-zine ring carrying at least one labile substituent and ~
is a bridging member which is linked to J and J through optionally substituted imino groups, said imino groups being linked together through an alkylene or arylene radical such as ethylene, 1:4 -phenylene or 2-sulpho-1:4-phenylene.

' .. . . . .

Other linking groups of particular interest represented by M are the divalent radicals of stilbene, diphenyl, diphenyloxide, diphenylamine, diphenylurea, diphenoxyethane and diphenylamino-s-triazine, which contain a sulphonic acid group in each benzene nucleus, It is preferred that Jl and J2 should each represent a chloro-s-triazine group, Thus, a further class of reactive dyestuffs comprises those dyestuffs which con-tain as the fibre-reactive group a group of the formula:

~ N \

N~ " N Cr_lH2r-1 ¦

C ~ (7) ~ I M ~ ~ ~ l - Cl ., , I ~
Cp lH2p 1 C lH2 :

wherein r, ~ and ~ are each independently 1 or 2, and M and - Q have the meanings stated above, The group Q, as previously defined, includes within its scope groups which contain a chromophoric system linked ~to the carbon atom of the triazine ring through -~H- or -O-. ~.
.~ ~ '.''' Such reactive dyestuffs can be obtained in conven- ;
tional manner for example by reacting a water-soluble dyestuff containing a primary or secondary amino group with a compound which contains the said fibre-reactive group As examples of such compounds there may be mentioned acryloyl chloride, cyanuric chloride, 2:4:6-trichloropyrimidine, 2:4:6-trichloro-5-(cyano- or chloro-)pyrimidine and 6-methoxy-2:4-dichloro-1:3:5-triazine, Other preferred reactive dyestuffs are those containing one or more phosphorus acid groups, particularly phosphonic acid groups, which are applied to cellulose textile materials by the methods described in U.K, Patent Specification ~o. 1411306.
By this process of the invention aromatic polyester/cellulose unions are coloured in a variety of shades which have excellent fastness to the tests commonly applied to such textile materials, and there is excellent reserve of the white unprinted portions of such textile materials, The preparation of certain coupling components and dyestuffs for the particularly preferred mixtures according to the present invention is described below, Parts are by weight unless otherwise indicated, the : ratio of parts by weight to parts by volume being that of the kilogram to the litre.

11C~1154 Preparation of 5-acetylamino-2-methoxy-N,N-diethylaniline 18 parts of 5-acetylamino-2-methoxyaniline are stirred in 50 parts by volume of water. Aqueous sodium hydroxide solution (70O Tw) is added to adjust the pH to 9-10, The mixture is heated to 65OC and a dispersing agent )polyglycerolricinoleate,0,5 part) is added followed by 29.4 parts of sodium bicarbonate (e~uivalent to 3,5 mols per mole of the aniline ...
starting material). 54 parts of diethylsulphate ~3,5 mols per mol of mol of starting material) is then added over a period of 2 hours at 65C, Reaction proceeded smoothly, Stirring of the mixture at 65C was continued for.a further 2 hours after addition of the diethyl-sulphate to complete the reaction. The reaction mixture . was cooled to room temperature and the 5-acetylamino-2-methoxy-~,~-diethylaniline was collected, washed with water (500 parts of volume) and dried at 70C, ~,~-Diethyl-m-aminoacetanilide is prepared in similar manner starting from m-aminoacetanilide, Preparation of the dyestuff _f formula (II) in which Xl ~.
is methoxy . .:
70 parts (by volume) of 100% sulphuric acid : are added to 4 parts of water, 7 parts of sodium nitrite are then added portionwise to the stirred acid .
at a rate such as to raise the temperature of the mixture to 70~ 2C and to maintain it at that level, : :
On completion of the addition of sodium nitrite.the - .
.' .

, ~.

, , . .

l~llS4 solution is stirred for 1 hour, the temperature being allowed to fall to room temperature 26 2 parts of 2,4-dinitro-6-bromoaniline are added to the stirred sodium nitrite solution at 25-28C during 30 minutes.
On completion of the addition the solution is stirred for 2 hours at room temperature.
23,6 parts of 5-acetylamino-2-methoxy-N,N-diethylaniline are stirred in 500 parts of water and 10 parts by volume o concentrated hydro-chloric acid are added. Ice is added to the solution to lower the temperature to 0C and anhydrous sodium acetate is added to adjust the pH to 3-4. The diazotised amine solution is then added dropwise during 30 minutes at 0C and pH 4 (controlled by the addition of ice and sodium acetate) until only a trace of excess coupling component remains as shown by testing the mixture with diazotised p-nitroaniline, The mixture is stirred for a further 15 minutes at 0-5C, and the dyestuff is collected and washed free from inorganic contaminants with water. The d~estuff is dissolved in boiling acetone, the solution is filtered and the dyestuff is re-precipitated by the addition of ice and water to the acetone solution. The product is again collected, washed with water and dried at 70C.
Preparation of the dyestuff of formula (II) in which X is hydroqen 2,4-Dinitro-6-bromoaniline (2~ 2 parts~ is diazotised and coupled with 20,6 parts of N,N-diethyl-m-aminoacetanilide exactly as described for the preceding preparation, ~lV1~54 The invention illustrated butnot limited by the following Examples in which parts and percentages are by weight Example 1 10 Parts of the dyestuffs o~ formula (II) in which W = Br, Xl = methoxy and W = Br, X = hydrogen respectively are individually gravel milled with 12.8 parts of an aqueous solution of a dispersing agent (sodium salt of a naphthalene-2- sulphonic acid/formal-dehyde condensate), containing 39 2% by weight of theagent, and 77 2 parts of water After 48 hours milling the particle size of each dyestuff in its dispersion is 3-4 microns ~ 0.3 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which,W = Br, X
hydrogen, and 0,075 part of the 10% aqueous dispersion .::
, of the dyestuff of formula (II) in which.W = Br, X
methoxy, both dispersions being obtained as described above, are transferred into a dyeing vessel. 0.5 part by volume of a buffer solution is added, followed by 5 parts of polyester piece textile material. The dye-bath is then made up to 50 parts with water and dyeing ~ is effected under superatmospheric pressure at 130C
:~ for 1 hour.
On completion of dyeing the dyed material is stirred in a reduction clearing bath comprising 5 parts of sodium hydrosulphite, 3 parts by volume of sodium hydroxide solution (70 Tw), 3 parts by volume of a dispersing agent and 490 parts by volume of water, for 30 minutes at 70C. The fibre is then thoroughly washed in a soap solution, rinsed well in water and .~.,~'i ll~llS4 and dried.
The polyester is dyed in a navy blue shade having very good build up and high tinctorial strength.
Example 2 - The dyeing procedure described in Example 1 is repeated except that the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl = H and the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl - methoxy are used in the following amounts:-(II W - Br,X - H(II)W = Br,Xl= methoxv (a) 0.10 0,30 (b) 0,20 0,20 (c) 0,25 0.15 :
(d) 0.30 0,10 (c) 0,35 0,05 In each case a strong navy blue shade on polyester textile material is obtained, Example 3 The dyeing procedure described in Example 1 is repeated except that the 0,075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X - methoxy is replaced by 0,1 part of a 10% aqueous dispersion of one of the following dyestuffs of formula (I), W, X, Y, Z and R in the table below have the same significance as in formula (I), lS4 W X Y Z R

ta) Br OCH3 CH3 CH3 CH3 (b) Br OCH3C3H7~n) C3H(n) CH3 (c) Br C4 9(-) C2H5 C2H5 CH3 (d) Br OCH3 C2H5 C2H5 C2H5 (e) Cl OCH3 C2H5 C2H5 3 (f) Br 0C2H5 C2H5 C2 5 : (g) Br 3 7(-1 C2H5 C2H5 3 (h) Br OCH3 C4Hg( ) C4Hg(~) CH3 (i) Br OCH3 CH3 C4H9(_) CH3 (j) Br OCH3 C2H5 C2H5 C3H7(n) (k) Br OCH3 C2H5 C2H5 C3H7 (i80) : Each dyestuff mixture when applied to aromatic ; polyester textile material as described in Example 1 gives a strong navy blue shade Example 4 The dyeing procedure described in Example 1 i9 repeated except that the 0, 075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = methoxy ~:20 is replaced by 0,1 part of the same dyestuff dispersion, and the 0.3~part of the 10% aqueous dispersion of the formula (II) ` ; ~ in which W = Br, X = hydrogen is replaced by 0.3 part of a :10% aqueous dispersion of one of the following dyestuffs of formula (I). W, X, Y, Z and R in the table below have the same significances as in formula (I).

,~

.

~l~tllS4 W X Y Z R

(a) Br 2 5 C2 5 C2H5 (b) Cl HC2H5 C2H5 CH3 (c) Br HCH3 CH3 CH3 (d) Br H3 7(_) C3H7(_) CH3 (e) Br HC4Hg(_)C4Hg ~) CH3 (f) Br HCH3 CH2cH(cH3) 2 CH3 ~`

(g) Br HC2H5 C2H5 C3H7 ~) Each dyestuff mixture when applied to aromatic polyester textile material as described in Example 1 gives a strong navy blue shade.
ExamPle 5 :, 0 3 part of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = hydro~en, 0.5 par~ of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, Xl = methoxy and 0.05 part of a 10% aqueous dispersion of the dyestuff of formula (II) in which W = Br, X = ethoxy are mixed together. This mixture when applied to aroma~ic polyester textile material by the method described in Example 1 gives strong navy blue shades.
~ ~ .
Similar results are obtained if the dyestuff of formula (II) in which W = Br, Xl = ethoxy is replaced by the dyestuff of formula (I) in which W is bromine, X is methoxy, Y and Z are each n-propyl and R is methyl.
Example 6 A mixture is made in the proportions given below, of the 10% aqueous dispersions of four dyestuffs of formula (I) in which Y and Z are each ethyl, R is methyl and W and X have the meanings given below -21- ~

~j :

, . , 110~

- x -Br H 1.5 part Cl H 1 5 part Br OCH3 0 5 part Cl OCH3 0.5 part This mixture when applied to aromatic polyester textile material by the method described in Example 1 gives strong navy blue shades.
Example 7 26.2 Parts of 2,4-dinitro-6~bromoaniline are diazotised by the method described previously and the diazonium compound so obtained is coupled with a mixture of 6.0 parts of 5-acetylamino-2-methoxy-~ diethyl-aniline and 15.4 parts of ~,~-diethyl-m-aminoacetanilide by the method described previously. The mixed dyestuff so obtained when applied in the form of an aqueous dispersion to aromatic polyester textile material as described in Example 1 gives strong navy blue shades Example 8 The dyeing procedure described in Example 1 is repeated except that the 0 3 part of a 10% aqueous dispersion of the dyestuff of formula (II~ in which W = Br, ~: .
~ xI = hydrogen is replaced by 0.3 part of a l~/o aqueous .
dispersion of the dyestuff of formula (II) in which W =
Cl, X ~= hydrogen, and the 0.075 part of the 10% aqueous dispersion of the dyestuff of formula (II) in which W -Br, X = methoxy is replaced by 0 1 part of a 10% aqueous dispersion of one of the following dyestuffs of formula (I~.

:
W, X, Y, Z and R in the table below have the same signifi-cance as iD formula (I) :
~ ~ -22-, llalls4 W X Y Z R
(a) Cl OCH3 C2H5 C2H5 CH3 (b) Cl C2H5 C2H5 C2H5 CH3 (c) Cl OCH3 C2H5 C2H5 C2H5 (d) Cl OCH3 C3H7(n) C3H7(_) CH3 Each dyestuff mixture when applied to aromatic polyester textile m~terial as described in Example 1 gives a strong navy blue shade.
ExamPle 9 A 67/33 woven blend of polyester/cotton fibres is padded in a pad-liquor of the following constitution, so that the material retains 50% of its weight of the padding liquor, 1 part of the dyestuff of formula (II) in which W = Br, X = hydrogen, as a 10% a~ueous dispersion, 4 parts of the dyestuff of formula (II) in which W = Br, X = methoxy, as a 10% aqueous dispersion, ~- ~ 10 parts urea, 10 parts Matexil FA-MIV (a migration inhibitor marketed by Imperial Chemical Industries Limited;
~ "Matexil" is a Registered Trade Mark) :~ 10 parts sodium bicarbonate per 1000 parts of : pad liquor The dyes are preferably in the form of an aqueous . ~ ~ dispersion, milled in the presence of an equal weight of : a protective agent such as the sodium salt of a naphthalene-2-sulphonic acid/formaldehyde condensate.

-23- :

.
, :~

:' ~.
,. ..

.

The padded material is dried for 30 seconds at 110C, baked for 60 seconds at 210C, rinsed in hot water, treated for 30 seconds at 80C in a solution containing 2 g/litre Synperonic BD (a synthetic detergent marketed by Imperial Chemical Industries Limited, "Synperonic" is a Registered Trade Mark) rinsed in cold water and dried.
The above series of operations can conveniently be carried out as a continuous sequence The polyester portion of the blend is dyed to a full, reddish navy shade while the cotton portion is only slightly stained, and the fabric has good fastness to light and washing.
Example 10 The padding procedure described in Example 9 is repeated except that the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the dyestuff of formula (II) in which W = Br, X = methoxy are used in the following proportions:-(II) W = Br, X = H (II) W = Br, Xl =
. M methoxy (a) 1 0 3.0 (b) 2,0 2.0 : ~c) 2,5 l S
: ~ (d) 3.0 1.0 : (e) 3.5 0 5 In each case a similar result to that describedin Example g is obtained Example 11 The padding procedure described in Example 9 is 30 repeated except that the 1 part of the dyestuff of formula :~
(II) in which W = Br, X = hydrogen.is increased to 3 parts, and the 4 parts of the dyestuff of formula (II) in which . -24-' ' ' ~ '.

11~115~

W = Br, Xl = methoxy are replaced by 1 part of one of the following dyestuffs of formula (I) W,X, Y, Z and R in the table below have the same significance as in formula (I).
W X Y z R
ta) Br OC~3 CH3 CH3 CH3 (b) Br OCH3 C3H7(n) . C3H7(n) CH3 (c) Br OC4Hg~) C2H5 C2H5 CH3 (d) Br OCH3 C2H5 C2H5 CH5 Cl OCH3 C2H5 C2H5 CH3 (f) Br C2H5 C2H5 C2H5 CH3 (g) Br OC3H7(_) C2H5 C2H5 CH3 (h) Bx OCH3 C4Hg(_) C4Hg ~) CH3 (i) Br OCH3 CH3 C4Hg(_) CH3 (i) Br OCH3 C2H5 C2H5 C3H7(n) (k) Br OCH3 C2H5 C2H5 c3H7(iso) In each case a similar result to that described in Example 9 is obtained.
Example 12 The padding procedure described in Example 9 is repeated except that the 4 parts of the dyestuff of formula (II) in which W = Br, Xl = methoxy are reduced to 1 part, and the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen is replaced by 3 parts of -one of the foll~wing dyestuff of formula (I). W, X, Y, Z and R in the table below have the same significance as - . ..... ................................................................... : .
in formula (I) . ,~' -W X Y Z R
(a) Br H 2 5 C2H5 C2H5 (b) Cl H C2~5 C2H5 CH3 (c) Br H CH3 CH3 3 (d) Br H C3H7(n) C3H7(_) CH3 (e) Br H C4Hg(_) C4H9(n) CH3 (f) Br H CH3 CH2CH(cH3)2 CH3 (g) Br H C2 5 C2Hs C3H7(n) In each case a similar result to ~hat described in Example 9 is obtained.

ExamPle-l3 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of ~ formula (II) in which W = Br, X = hydrogen and the 4 I ~ parts of the dyestuff of formula (II) in which W = Br, xl = methoxy are replaced by 3 parts of the dyestuff of formula (II) in which W = Br, Xl = hydrogen, 0.5 part of the dyestuff of formula (II) in which W = Br, X
methoxy and 0.5 part of the dyestuff of formula (II) in which W = Br, Xl = ethoxy.
A similar result to that described in Example 9 is obtained.
If the dyestuff of formula (II~ in which W = Rr, X = ethoxy is replaced by the same amount of the dyestuff ., ~
of formula (I) in which W is hromine~ R is methyl, X is methoxy, and Y and Z are each n-propyl, a similar result is obtained.

. ~ .
~ -26-~ ' ' .

Example 14 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the 4 parts of the dyestuff of formula (II) in which W = Br, Xl =
methoxy are replaced, in the proportions given below, by four dyestuffs of formula (I) in which Y and Z are each ethyl, R is methyl and W and X have the meanings given below:-W X
Br H 1.5 parts Cl H 1.5 parts Br OCH3 0.5 parts Cl OCH3 0.5 parts : A similar result to that described in Example 9 is obtained.
Example 15 A mixture of dyestuffs of formula (II) in which W = Br, Xl = hydrogen and W = Br, Xl = methoxy respectively is prepared as described in Example 7 and converted into 10% aqueous dispersion.
When this dispersion is applied to a polyester/
cotton blend as described in Example 9 a similar result is obtained, Example 16 The padding procedure described in Example 9 is repeated except that the 1 part of the dyestuff of formula (II) in which W = Br, Xl = hydrogen and the 4 parts of the dyestuff of formula (II) in which W = Br, Xl = methoxy are r placed by 3 parts of the dyestuff of ' l~llS4 formula (II) in which W = C1, Xl = hydrogen and 1 part of one of the following dyestuffs of formula (I) respectively.
W, X, Y, Z and R in the table below have the same signifi- -cance as in formula (I), W X Y Z R
(a) C2H5 C2H5 ~H3 (b) Cl C2H5 C2H5 C2H5 CH3 (c) Cl OCH3 C2H5 C2H5 C2H5 (d) Cl OCH3 C3H7~_) C3H7(-) CH3 In each case a result similar to that described in Example 9 is obtained.

-...

' ~ .

'

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A mixture of two or more disperse monoazo dyestuffs of the formula:
wherein W is a chlorine atom or a bromine atom;
X is hydrogen or OR1 and R, R , Y and Z are lower alkyl groups, provided that the mixture contains at least one component in which X = H and another in which X - OR1,

2. A dyestuff mixture as claimed in claim 1 which comprises two components in amounts from 95:5 to 5:95 parts by weight.

3. A dyestuff mixture as claimed in claim 2 which comprises the two components in amounts from 80:20 to 20:80 parts by weight.

4. A dyestuff mixture as claimed in claim 1 which comprises two dyestuffs selected from dyestuffs having the formula:

in which W is a chlorine atom or a bromine atom and X1 is either hydrogen, or methoxy or ethoxy, provided that in one component of the mixture X1 is hydrogen and that in the other component X1 is methoxy or ethoxy.

5. A dyestuff mixture as claimed in claim 4 wherein the dyestuff in which X1 is hydrogen and the dyestuff in which X1 is methoxy or ethoxy are in the proportions between approximately 4:1 and approximately 2:1 by weight, respectively.

6. A dyestuff mixture as claimed in claim 4 which comprises the two dyestuffs in which W is bromine and X1 is hydrogen, and in which W is bromine and X1 is methoxy, in the proportions of approximately 3:1 by weight, respectively.

7. A process for the colouration of aromatic polyester textile materials and aromatic polyester/cellulose unions which comprises applying to the said textile material or union by an aqueous dyeing, padding or printing process a mixture of two or more disperse monoazo dyestuffs as claimed in claim 1.

8. A process as claimed in claim 7 wherein the mixture of two or more disperse monoazo dyestuffs is applied to an aromatic polyester/cellulose union in con-junction with one or more colouring matters for the cellulose component of the union

9. A process as claimed in claim 8 wherein the colouring matter for the cellulose component of the union is a Direct Dyestuff, Vat Dyestuff, Sulphur Dyestuff, Azoic Colouring Matter or Reactive Dyestuff.

10. A process as claimed in claim 9 wherein the coloring matter for the cellulose component of the union is.
a reactive dyestuff which contains as the fibre-reactive group a heterocyclic radical having two or three nitrogen atoms in the heterocyclic ring and at least one labile substituent attached to a carbon atom of the heterocyclic ring,

11. A process as claimed in claim 10 wherein the reactive dyestuff contains a triazine or pyrimidine ring containing as the labile substituent at least one chlorine, bromine or fluorine atom

12. A process for the manufacture of the mixtures of disperse monoazo dyestuffs claimed in claim 1 which comprises coupling a mixture of at least two coupling components of formula:

wherein R,X, Y and Z have the meanings stated in claim 1, with at least one diazonium compound obtained by diazotisation of an amine of formula:

wherein W has the meaning stated in claim 1, provided that the mixture of coupling components contains at least one component in which X is hydrogen and at least one component in which X
is OR1.